Process for preparing color film with auxiliary or silver sound record using bleach inhibitor

ABSTRACT

A PROCESS IS PROVIDED FOR PREPARING COLOR FILM HAVING A SILVER AUXILIARY OR SOUND RECORD WHICH COMPRISES CONTACTING ONLY THE AUXILIARY OR SOUND RECORD AREA OF AN EXPOSED FILM HAVING SUCH A SILVER IMAGE SUBSEQUENT TO INITIAL DEVELOPMENT, AND PRIOR TO BLEACHING WITH A SILVER BLEACH INHIBITOR.

Dec. 12, 1912 M ms m1. 3,105,803

PROCESS FOR PREPARING COLOR FILM WITH AUXILIARY OR SILVER SOUND RECORD USING BLEACH INHIBITOR Filed Dec. 17, 1971 1 1 Z LSUPPOR? ORIGINAL 2/- k 1 R1 IMAGE v V Jr W {I 25 I "GREEN-SENSITIVE, MAGENTA FORMING LAYER 24 j RED-5E/vs/T/vE,cYA/v FORM/N6 LAYER BLUE- SENSITIVE, YELLow FORM/N6 LAYER STAGE 2 28 '250 GREEN RECORD, SILVER AND MAGENTA IMAGE 24a RED RECORD, SILVER AND CYAN IMAGE 23g -BLUE RECORD, SILVER AND YELLOW IMAGE 22//// T-su PoRr GREEN REcoRD, sou/v0 REcoRD PROTECTED 25b 6mm. 1 BY BLEACH INHIBITOR RED REcoRD, sou/v0 REcoRD RRorEcrED BY DLEAcH INHIBITOR BLUE RECORD SUPPOR 7' GREEN REcoRD, MAGENTA DYE IMAGE, 2 s/L vER sou/VD RECORD RED REcoRD, cYA/v DYE IMAGE, :3 slLvER SOUND RECORD BLUERECORD, YELLOW DYE IMAGE,

LSUPPORT MICHAEL .L BEV/S HOBSON J BELLO cARL E HOL7'Z INVENTOR.

BY @A A DAM A T TORNE Y United States l atent O PROCESS FOR PREPARING COLOR FILM WITH AUXKLIARY OR SILVER SOUND RECORD USING BLEACH INHIBITOR Michael .I. Bevis, Wealdstone, Harrow, England, and Hobson J. Bello and Carl F. Holtz, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y.

Continuation-impart of abandoned application Ser. No. 100,608, Dec. 22, 1970. This application Dec. 17, 1971, Ser. No. 209,459

Int. Cl. G03c 5/44, 7/24 US. Cl. 96-4 31 Claims ABSTRACT OF THE DISCLOSURE A'process is provided for preparing color film having a silver auxiliary or sound record which comprises contacting only the auxiliary or sound record area of an exposed film having such a silver image subsequent to initial development, and prior to bleaching with a silver bleach inhibitor.

This application is a continuation-in-part of Bevis et al. US. patent application Ser. No. 100,608, filed Dec. 22, 1970, and now abandoned.

This invention relates to color photographic films having metallic silver auxiliary images, sound tracks and more particularly to processes useful in preparing such films.

Color motion picture films having silver auxiliary images and sound tracks are well known. Typically, the color images are prepared by the three-color system of photography. In this well known system, color images are formed from three subtractive dyes: a yellow dye to control blue light, a magenta dye to control green light and a cyan dye to control red light. These dye images can be formed by various methods.

For example, color images can be produced by the dyebleach process. This process uses a film which has incorporated therein, in three separate layers, each sensitive to a primary color region of the visible spectrum, a pre-- formed subtractive dye which is capable of being destroyed in proportion to the silver formed upon development of a latent photographic image.

Another method of preparing a three-color record by the subtractive dye process is to photographically record an image in a photographic element having three photographic silver halide layers in a superposed relationship to each other, each layer being sensitive to essentially one primary color region of the visible spectrum. These photographic silver halide layers can contain photographic color couplers which form, upon coupling with oxidized aromatic primary amine color developing agent, subtractive dyes essentially complementary to the primary color regions of the visible spectrum. These photographic silver halide layers can, alternatively, not contain photographic color formers; the color image then being produced by processing in a coupler-developer composition to form nondiifusible subtractive dyes. Subsequent to dye image formation the developed silver and the residual silver halide must be removed from the picture area. This is usually accomplished by bleaching and fixing or by bleach-fixing (single step bleaching and fixing).

Optical motion picture sound tracks are printed onto the same film on which the picture image was printed. Optical sound tracks can be of the variable density or variable area types. The sound track itself can be comprised of dyes, dyes plus silver, silver compounds, silver plus other metals or silver alone. The photocell inmotion picture projectors used almost universally to detect light passing through an optical sound track is of such 3,705,803 Patented Dec. 12, 1972 nature that it is most sensitive to electromagnetic radiation of a wavelength greater than 700 nanometers (nm.) with a peak sensitivity at about 800 nm. The subtractive dyes which form the picture image have regions of maximum absorption from 400 to 700 nm. Consequently, these dyes are nearly transparent to infrared radiation and have very little modulating effect upon this radiation to which the photocell is most sensitive.

Silver produced as a result of the chemical reduction of a latent silver halide image is uniformly opaque to the full spectrum of radiation ranging from ultraviolet through visible into the infrared region and acts as an excellent modulator for infrared radiation to which current optical photocells are most sensitive. Silver compounds such as silver sulfide aud silver toned with metals such as gold are also more opaque than image dyes to infrared radiation. It can thus be seen it is preferably that optical sound records in color motion picture films be comprised of substances other than subtractive image dyes. The presence of subtractive dyes in addition to the other substances, however, is not objectionable.

As noted above, the developed silver and the residual silver halide must be removed from the picture area of a color motion picture film subsequent to color image formation. At the same time developed silver or a silver compound must be retained in the sound track area if the color motion picture film is to have the preferred sound track. A number of techniques have been devised to retain silver in the sound track area of color motion picture films during bleaching and fixing of the silver and residual silver halide in the picture area. For example, the sound track area can be covered with a varnish subsequent to formation of the picture and sound track images and prior to silver and silver halide removal. The varnish prevents diflFusion of the bleaching solution into the sound track area. Subsequent to rehalogenation of the silver in the picture area the varnish is removed with a suitable solvent and silver halide is removed from the entire film, reference being made to US. Pat. 1,973,463, issued Sept. 11, 1934 and US. Pat. 2,113,329, issued April 5, 1938.

A currently used method of retaining metallic silver in the sound track area is to print the picture and sound track images in the photographic silver halide element and develop the latent image to metallic silver. In print films the residual silver halide is removed by fixing the entire film. In reversal films only the sound track area is fixed followed by color reversal development. At this point both types of film have a sound track of metallic silver free from residual silver halide. The metallic silver is then converted to a fixable silver salt by bleaching both the sound track and picture areas. In the sound track area the silver salt is reconverted to metallic silver by applying a viscous, highly active developer, for example, by known striping techniques. Subsequently, the silver salt in the picture area is removed by fixing.

Another method of preventing the removal of the silver sound track is to treat the silver metal with a solution which produces a gold tone. This gold-toned silver metal is not removed upon bleaching and fixing, reference being made to US. Pat. 2,263,009, issued Nov. 18, 1941.

Still another method is to stripe the sound track area of the film with a quaternary ammonium salt which renders the silver metal unbleachable, reference being made to US. Pat. 3,243,295, issued Mar. 29, 1966. These quaternary salts are not bleach inhibitors within the meaning of the. term as defined below.

Still another method of retaining silver metal in the sound track area is to prepare a photographic multilayer element which forms a dye in the upper layer during chromogenic development which dye is reducible to a leuco dye which can reduce silver ions in solution to silver metal. The developed sound area is striped with Water and passed through a sulfur dioxide gas atmosphere where the gas is absorbed only in the moistened sound track area. The absorbed gas reduces the dye to a leuco dye. The film is then passed through an ammonia-silver nitrate solution where the leuco dye reduces silver ions to silver metal which is deposited in the film, reference being made to US. Pat. 2,286,747, issued June 16, 1942.

Alternatively, the silver in the sound track area can be converted to compounds or complexes which resist the bleaching of the silver. For example, silver or silver halide can be converted to silver sulfide prior to bleaching. The sulfide is not converted to a fixable silver salt by bleaching and thus remains as silver sulfide following fixing, reference being made to U.S. Pat. 2,143,787, issued Jan. 10, 1939. The treatment solution can contain both sulfiding and iodizing compounds, which also convert the silver to a compound which is not removed upon bleaching and fixing, reference being made to US. Pat. 2,258,976, issued Oct. 14, 1941.

Still another method of preparing a sound track is to coat a separate layer on the back of the film support. Each of the two sides of the film is processed without contacting the other side with the processing solutions, reference being made to US. Pat. 2,235,033, issued Mar. 18, 1941.

The above techniques refer to only a portion of the patented or known methods or refinements for producing silver or silver complex sound tracks in color motion picture films.

All of the above approaches entail certain disadvantages such as critical concentrations, critical times, long treatment times, a number of treatments to only one area of the film, extra treatment steps, special processing equipment, inadequate silver retention or the use of silver sulfide which is less absorbent of infrared radiation than silver. It, therefore, appears desirable to provide a method of retaining the silver of the optical sound record during the processing of color films which avoid the problems inherent in these techniques and yet provides a high quality sound record.

Accordingly, it is an object of our invention to provide a new method of preparing color photographic films having silver auxiliary images or silver sound records.

Another object of our invention is to provide a novel and improved method for the processing of exposed color films having an optical silver sound record.

A further object of our invention is to provide a novel and improved method for retaining the silver image of the sound record of color films during processing of the color film.

Other objects will become apparent from the following specification and appended claims.

These and other objects of this invention can be attained by contacting just the auxiliary silver image of a photographic film with a silver bleach inhibitor prior to bleaching. Contacting the auxiliary silver image with the bleach inhibitor results in the adsorption of the bleach inhibitor onto the silver image. Any suitable means can be used to contact the auxiliary silver image with bleach inhibitor, without contacting any other silver image in the photographic film with the bleach inhibitor. Such means include striping bleach inhibitor on just the area of the film containing the auxiliary silver image, and the special processes for selectively contacting auxiliary silver images with bleach inhibitor described and claimed in the Holtz; Bello and Holtz; and, Lestina, Kent and Holtz U.S. patent applications referred to below.

We have found that when a developed silver image is contacted with such a bleach inhibitor subsequent to initial development and prior to bleaching, the silver is rendered unbleachable. The silver in the picture area of the film not contacted with the bleach inhibitor remains bleachable. A color film having been so treated will upon bleaching and fixing comprise a picture record of dye images and a sound track record of silver images. Our invention, therefore, provides. a method for retaining image silver in the sound track area of the film during subsequent processing treatments to the entire film such as bleaching out silver in any filter layers that can be present and in the picture image area of the film.

The method of our invention includes a treatment of just the sound track portion of the film to selectively retain the silver sound image. For negative-positive print films the method offers the advantage of a single treatment to the silver sound record. Unlike the redevelopment process in current use, the film does not have to be fixed before bleaching. Subsequent to initial development the silver sound track record is contacted with a solution containing a silver bleach inhibitor. The film is then bleached and fixed or bleach-fixed. A reversal film is black and white developed followed by selective fixing of only the sound track area. The film is then reversal color developed. At this time the silver sound track record is contacted with a solution containing a silver bleach inhibitor. The entire film is then bleached and fixed or bleach-fixed. The processed films then comprise a color picture record and a silver sound record.

If desired, for example, to aid in silver recovery, print films can be fixed prior to bleach-fixing since silver is more easily recovered from fix solutions than from pres ent bleach-fixing solutions. If this procedure is used, it is preferred that the sound record be contacted with the bleach inhibitor subsequent to the fixing treatment.

The present invention, therefore, provides a convenient single step method for retaining a silver sound record in a color motion picture film during removal of the silver of the picture record. The method is particularly convenient since it involves merely contacting the film with a solution containing a silver bleach inhibitor. The contacting procedure is not dependent upon critical concentrations, times or temperatures. For example, the concentration of bleach inhibitor in a bleach inhibitor treatment solution used in the invention can range from as little as 10 molar or less to molar or more. Preferably, the concentration of bleach inhibitor ranges from about 10 to about 10- molar. The concentration of bleach inhibitor in treatment compositions can vary depending upon the particular bleach inhibitor. For example, the concentration of bleach inhibitor can vary depending upon the hydrophilic nature of the bleach inhibitor. We have found that higher concentrations of the more hydrophilic bleach inhibitors yield better results. On the other hand, less hydrophilic bleach inhibitors, e.g., those substituted with medium to long alkyl chains, often yield satisfactory results at lower concentrations.

The time the bleach inhibitor is in contact with the silver sound record prior to being brought into contact with another processing solution can vary widely. It typically ranges from as little as 5 seconds or less to 10 minutes or more. Preferably, the film is contacted with bleach inhibitor for about 30 seconds to about 5 minutes. The contact time for optimum results also can depend upon the hydrophilic nature of the bleach inhibitor and its rate of diffusion through the sound track emulsion layers. Hydrophilic bleach inhibitors can require a longer contact time to insure good coverage of the silver sound image. Slowly diffusing bleach inhibitors can also require a longer contact time to insure adequate penetration of the emulsion layers.

The temperature at which the bleach inhibitor can be brought into contact with the silver sound record can vary widely, but preferably is approximately the same as the temperature of the remainder of the processing solutions. For example, photographic processing temperatures typically range from about C. or less to 60 C. or higher. Temperatures of about C., C. and C. are quite common in modern high speed processing procedures. Since the method of our invention is dependent upon physical contact with and probably adsorption onto the silver sound image, the contact temperature is not critical as it can be in other methods. The determination of the proper combination of the above variables can readily be determined for the particular bleach inhibitor to be used by one skilled in the photographic art.

As used herein and in the appended claims, the term bleach inhibitor refers to an organic compound which, when dissolved in an aqueous solution at a concentration of 10- molar and mixed with an equal volume of a 0.05% w. aqueous gelatin solution containing a concentration of 3 l0- molar silver metal particles of about 0.12 micron in diameter, which silver particles are prepared by contacting a silver nitrate solution with equal molar amounts of sodium citrate and ferrous sulfate (as described by Frens, The Reversibility of Irreversible Colloids Ph. D. Thesis, University of Utrecht, Holland, 1968, p. 27), inhibits bleaching for a minimum of 15 minutes when there is added to the mixture of silver particles and bleach inhibitor one volume of the following bleach-fix bath:

BLEACH-FIX BATH I NaFeEDTA 1 (13% Fe) grams 6.0 Na SO do 1.2 Na EDTA do 0.7 (NH S O (60% solution) ..ml 20 Water to 1 liter.

1 EDTAEthylenediamlne tetraacetlc acid.

HO CH2C CHCOOH N-CHg-CHz-N HOOC-HzC UHF-CODE Bleach-fixing occurs when the mixture changes from dark brown to colorless. A control solution which contains no bleach inhibitor becomes colorless within four minutes.

We have found that organic compounds which exhibit particular utility as bleach inhibitors as defined above are thioand seleno-containing compounds such as mercaptoand selenol-substituted alkanoic acids, especially 2-mercaptoalkanoic acids, thioland selenol-substituted aryls, such as thiophenols and thionaphthols, thioland selenolsubstituted heterocyclic compounds containing 5 to 6 atoms in the hetero ring, said ring containing at least one nitrogen atom such as mercaptobenzoxazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiodiazoles, mercaptotriazoles, 1-phenyl-5-mercaptotetrazoles and mercaptoquinolines, thiocarboxylic acids and esters thereof such as thiobenzoic acid and xanthates such as potassium octyl xanthate.

In a preferred embodiment of our invention, the term bleach inhibitor refers to a compound of the following general formulae:

a represents 0, l, 2, 3, 4, 5 or 6;

-X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represents a member selected from the group consisting of nitro; halo (e.g., chloro, bromo, fiuoro, iodo); an alkyl group including substituted alkyl having from 1 to 22 carbon atoms, preferably having 1 to 16 carbon atoms such as alkyl (e.g., methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, pentyl, iso-amyl, tert-amyl, cyclopentyl, hexyl, cyclohexyl, cyclohexadiene, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and the like), haloalkyl (e.g., fluoroalkyl, chloroalkyl, bromoalkyl, as for example, chlorooctyl, bromododecyl, fluorotetradecyl and the like, sulfoalkyl (e.g., sulfohexyl, sulfooctyl, sulfododecyl and the like), sulfatoalkyl (e.g., sulfatodecyl, sulfatotetradecyl and the like),

alkylsulfonylalkyl (e.g., ethylsulfonylbutyl and the like), cyanoalkyl (e.g., cyanohexyl, cyanooctyl, cyanodecyl and the like), carboxyalkyl (e.g., carboxyhexy, carboxydecyl, carboxylhexadecyl and the like), aralkyl (e.g., benzyl, phendodecyl, tolyldodecyl and the like), alkoxyalkyl (e.g., octoxyhexyl, butoxyhexyl, ethoxydccyl and the like), aryloxyalkyl (e.g., phenoxymethyl, phenoxyethyl and the like), alkoxyaralkyl (e.g., methoxyphenylmethyl, butoxyphenylhexyl and the like), acyloxyalkyl (e.g., benzoyloxyhexyl, acetoxybutyl and the like), alkoxycarbonylalkyl (e.g., butoxycarbonylhexyl and the like), aryloxycarbonylalkyl (e.g., phenoxycarbonylethyl, chlorophenoxycarbonylbutyl and the like), alkylamidoalkyl (e.g., hexanamidobutyl, octanamidopropyl and the like), arylamidoalkyl (e.g., phenylamidoethyl, methylphenylamidobutyl and the like) and the like; an aryl group including naphthyl and other fused ring aromatics and substituted aryl such as aryl (e.g., phenyl, naphthyl, anthracenyl, phenanthrenyl and the like), haloaryl (e.g., chlorophenyl, trichlorophenyl, dibromophenyl, fiuorophenyl, chlorotolyl and the like), sulfoaryl (e.g., sulfophenyl and the like), sulfatoaryl (e.g., sulfatophenyl and the like), nitroaryl (e.g., nitrophenyl, dinitrophenyl and the like), cyanoaryl (e.g., cyanophenyl, cyanonaphthyl and the like), carboxylaryl (e.g., carboxyphenyl, dicarboxyphenyl and the like), alkaryl (e.g., tolyl, butylphenyl, decylphenyl, diethylphenyl, trifiuoromethylphenyl and the like) aralkaryl (e.g., benzylphenyl, naphthylmethylphenyl and the like), alkoxyaryl (e.g., octoxyphenyl, methoxyphenyl and the like), aryloxyaryl (e.g., phenoxyphenyl, phenoxynaphthyl and the like), acyloxyaryl (e.g., benzoyloxyphenyl, acetyloxyphenyl and the like), alkoxycarbonylaryl (e.g., ethoxycarbonylphenyl and the like), aryloxycarbonylaryl (e.g., phenoxycarbonylphenyl, methylphenoxycarbonylnaphthyl and the like), alkylamidoaryl (e.g., acetamidophenyl, amylamidophenyl, di-t-amylamidophenyl, hexanamidohenyl, heptanamidophenyl, octanamidophenyl, nonanamidophenyl, decanamidophenyl, undecanarnidophenyl, dodecanamidophenyl, tridecanamidophenyl, tetradecanamidoaryl, pentadecanarnidophenyl, heptafluorobutanamidophenyl, carboxycyclopentanacetamidophenyl and the like), cycloalkyliminosulfonylaryl (e.g., piperidinylsulfonylphenyl, azetidinylsulfonyphenyl, pyrroidinylsulfonylphenyl, indolinylsulfonylphenyl and the like) and the like; a thio group containing 3 to 22 carbon atoms such as alkylthio (e.g., propylthio, hexylthio, octylthio, dodecylthio and the like), carboxyalkylthio (e.g., carboxybutylthio, carboxyhexylthio and the like), arylthio (e.g., phen ylthio, naphthylthio, methylphenylthio and the like), alkylcarbonylalkylthio (e.g., methylcarbonylethylthio, butylcarbonylpropylthio and the like), alkylcarbonylarylthio (e.g., methylcarbonylphenylthio, hexylcarbonyltolylthio, benzylcarbonylphenylthio and the like), arylcarbonylarylthio (e.g., phenylcarbonylphenylthio and the like), arylcarbonylalkylthio (e.g., phenylcarbonylmethylthio and the like), and the like; an amido group containing from 4 to 22 carbon atoms such as alkylamido (e.g., hexanamido, heptanamido, octanamido, decanamido, heptafiuorobutanamido and the like), arylamido (e.g., benzylamido and the like), alkarylamido (e.g., methylbenzylamido, butylbenzylamido, hexylbenzylamido, decylbenzylamido and the like), aralkylamido (e.g., phenacetamido, phenbutanamido, tolylhexanamido and the like), aryloxyalkylamido (e.g., phenoxyacetamido, naphthoxyacetamido, di-t-amylphenoxyacetamido and the like) and the like; a carbonyl group such as alkylcarbonyl (e.g., butylcarbonyl, heptyl carbonyl and the like), arylcarbonyl (e.g., phenylcarbonyl, naphthylcarbonyl and the like, alkoxycarbonyl (e.g., ethoxycarbonyl, butoxycarbonyl and the like), aryloxycarbonyl (e.g., phenoxycarbonyl, naphthoxycarbonyl and the like) and the like; a carbamoyl group such as alkylcarbamoyl (e.g., butylcarbamoyl; hexyicarbamoyl and the like), arylcarbamoyl (e.g., phenylcarbamoyl, naphthylcarbamoyl and the like) and the like; alkoxy (e.g., ethoxy, butoxy, octoxy, benzoxy and the like); and aryloxy (e.g., phenoxy, toluoxy and the like);

R represents a member selected from the group consisting of hydrogen and an acyl group having from 1 to 22 carbon atoms including aryloyl and alkanoyl groups (e.g., benzoyl, acetyl, propanoyl, benzothioyl, acetothioyl and the like);

Y represents a basic cation such as an alkali metal ion like sodium and potassium, ammonium and the like;

A A A and A each represents a member selected from the group consisting of a carbonyl group C=O); a thiocarbonyl group C=S); a carboxymethylene group CH-COOH); a carbocyclic ring containing 3 to 6 carbon atoms which can be part of a fused ring structure such as cycloalkylene (e.g., cyclopropylene, cyclobutylene, cyclopentylene and cyclohexylene), cycloalkenylene (e.g., cyclopropenylene, cyclobutenylene, cyclopentenylene, cyclopentadienylene, cyclohexenylene and cyclohexadienylene) and arylene (e.g., phenylene, naphthylene, anthrylene and the like; a 3 to 6 membered heterocyclic ring containing at least one carbon atom and from 1 to 5 atoms selected from the group consisting of .nitrogen, oxygen, sulfur and selenium which ring can have other carbocyclic and heterocyclic rings fused to it such as oxirenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, oxazolyl, benzoxazolyl, isoxazolyl, benzisoxazolyl, oxadiazolyl, benzoxadiazolyl, 1,2-pyranyl, 1,4- pyranyl, 2(H)benzopyranyl, 4(H)benzopyranyl, dioxolyl, methylenedioxybenzene, 1,2-oxazinyl, 1,3-oxazinyl, 1,4- oxazinyl, morpholinyl, 1,3-dioxolanyl, 1,3-oxathianyl, 1,4- oxathianyl, 1,2-dioxanyl, 1,3-dioxanyl, 1,4-dioxanyl, dioxanenyl, dioxadienyl, diazetyl, pyrrolyl, indolyl, isoindolyl, carbazolyl, pyrrocolinyl, acridinyl, phenanthridinyl, 2-imidazolinyl, 3-imidazolinyl, 4-imidazolinyl, pyridyl, pyridazinyl, cinnalinyl, phthalazinyl, quinoxalinyl, pyrimidinyl, pyrazolo[3,4d]pyrimidinyl, hypoxanthinyl, benzopyrimidinyl, pyrazinyl, quinoxalinyl, phthalazinyl, quinolinyl, isoquinolinyl, phenazinyl, phenoxazinyl, phenothiazinyl, purinyl, pteridinyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, triazolyl, benzotriazolyl, tetrazolyl, triazinthionyl, 1(H)azepinyl, piperidinyl, imidazolidinyl, quinolizidinyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, thiazolyl, benzothiazolyl, isothiazolyl, benzisothiazolyl, thiadiazolyl, benzothiadiazolyl, 1,2-dithiolyl, 1,3-dithiolyl, 1,3-oxathiolyl, thianthrinyl, thiamorpholinyl, 1,4-thianinyl, 1,4-dithanyl, 1,4-dithiadienyl, selenazolyl, benzoselenazolyl, isoselenazolyl, benzisoselenazolyl, sel enadiazolyl, benzoselenadiazolyl and the like; such that R R R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent carbonyl or thiocarbonyl and such that the grouping R (A the grouping R (A the grouping R (A and the grouping R -(A each represents a moiety having a molecular weight of from 100 to 1,000 and preferably from 125 to 400 and preferably containing not more than one solubilizing group such as carboxy unless the grouping contains a hydrophobic moiety such as a long alkyl chain or an aryl group.

Many heterocyclic compounds having a molecular weight of less than 100 (exclusive of the mercapto group) such as those compounds shown in British Pat. 1,138,842 have been found not to be bleach inhibitors but rather bleach accelerators. Compounds of this type do not fall within the meaning of the term bleach inhibitor as defined below.

In a more preferred embodiment of our invention, the bleach inhibitor is an organic compound or the salt of an organic compound as defined in Formulae I, II and III above having an acidic thiol or selenol, or having a group capable of forming such a compound prior to or subsequent to being brought into contact with a photographic element. For example, such thiol and selenol precursors can form the thiol or selenol group upon hydrolysis. Examples of precursors which form acidic thiol bleach. inhibitors are bleach inhibitors LXXXIII and LXXXIV. Another example of thiol forming compounds are disulfides (i.e., compounds of Formula II above) which cleave at the sulfur atoms to yield at least one thiol compound.

The acidity of the thiol and selenol groups can be imparted by the group to which these groups are attached (e.g., a heterocyclic or carbocyclic ring). Alternatively, other groups attached to the group having the thiol and selenol groups can impart acidity. For example, a carboxylic acid group on a carbon atom adjacent to the atom to which these groups are attached (e.g., 2-rnercaptolauric acid) imparts the desired acidity. Other electron withdrawing groups (e.g., nitro and halo) can also impart acidity t0 the thiol and selenol groups.

Compounds having the following formulae exhibit particular utility as bleach inhibitors:

(IV) Z-mercaptobenzoxazoles Mar rim (V) 2-mercaptobenzothiazoles l ufljt (VI) Z-mercaptobenzimidazoles (VII) Z-mercaptothiadiazoles N HS-() 8 (VIII) 2-mercaptotriazo1es l N HIS-i l- H (IX) 1-phenyl-5-mercaptotetrazoles (I) 4-hexanamidothiobenzoic acid ('11) 2-mercaptolauric acid (III) n-butyl-2-mercaptoacetate (IV) Z-mercaptoacetanilide (V) n-butylthiobenzoic acid (VI) 4-methylthiobenzoic acid (VII) 4-octylthiobenzoic acid (VIII) potassium octyl xanthate (IX) 2,4,S-trichlorothiophenol (X) 2-naphthalenethiol (XI) 4butyl-2-naphthalenethiol (XII) 2-quinolinethiol (CXXKIX) 4-ethylacridin-2-ylthiol (CXL) Z-phenanthridinylthiol (CXLI) 3-ethyl-4-butanamido-Z-imidazolin-Z-ylthiol (CXLII) 1,3-benzimidazol-2-thiol (CXLIII) fi-acetamido-1,3-benzimidazol-2-thiol (CXLIV) 6-pentanamido-1,3-benzimidazol-2-thiol (CXLV) 6-hexanamido-1,3-benzimidazol-2-thiol (CXLVI) 6-heptanamido-l,3-benzimidazol-2thiol (CXLVII) 6-octanamido-1,3-benzimidazol-2-thiol (CXLVIII) 6-nonanamido-1,3-benzimidazol-2-thiol (CXLIX) 6-decanamido-l,3 benzimidazol-2-thiol (CL) 6-undecanamido-l,3-benzimidazol-2-thiol (CLI) 6-dodecanamido-l,3-benzimidazol-2-thi0l (CLII) S-acetamido-1,3-benzimidazol-2-thiol (CLIII) -pentanamido-1,3-benzimidazol-2-thiol (CLIV) 5-octanamido-1,3-benzimidazol-2-thiol (CLV) S-decanamido-1,3-benzimidazol-2-thiol (CLVI) 4-butyl-2-pyridinylthio1 (CLVII) 4-(3-hexananamidophenyl)-2-pyridazinylthiol (CLVIII) 7-methylhypoxanthin-6-ylthiol (CLIX) 3-(3-hexanamidophenyl)-pyrazin2-ylthiol (OLX) 3-butylquinoxalin-2-ylthiol (CLXI) l-methylphthalazin-4-ylthiol (CLXH) 5-benzylamidophenylquinolin-2-ylthiol (CLXIII) 5-butylphenazin-2-ylthiol (CLXIV) 5-methylphenoxyazin-Z-ylthiol (CLXV) S-chlorophenothiazin-2-ylthio1 (OLXVI) S-n-decylthio-1,2,4-triazin-3-ylthiol (CLXVII) 5-(3-octanamidophenyl)-6-benzotriazolylthiol (CLXVIII) 4-butyl-lH-azepin-Z-ylthiol I (CLXIX) 1-(3-phenylpropyl)-2-piperidinylthiol (CLXX) l,3-dihexyl-Z-imidazolidinylthiol (CLXXI) 2-octy1thio-5-thienylthiol (OLXXII) 5-hexanamido-2-benzothienylthiol (CLXXIII) 5-octylthio-2-thiazolylthio1 (CLXXIV) S-butanamido-l,2,3-benzothiadiazol-6- ylthiol (CLXXV) 4-(3-hexanamidophenyl)-1,3-dithiol-2- ylthiol (CLPQCVI) 4- (3 -octanamidophenyl) l ,3-oxathiol-2- ylthiol (C-LXXVII) 4-hexyl-3-thiamorpholinylthiol (CLXXVIII) 4-(4-phenylbutyl)-1,4-thianin-3-ylthiol (CLXXIX) 4-(3-octanamidophenyl)-2-selenazolylthiol (CLXXX) S-benzamido-2-benzoselenazolylthiol (CLFOiXI) 5-acetamido-3-benzoisoselenazolylthiol CLXXXII) 4- 3-hexanamidophenyl) -3 -isoselenazolylthiol (OLXXXIII) 4-arnylamido-2,1,3-selenadiazol-5- ylthiol (CLXXXIV) 4- (Z-nitrophenyl -2, 1 ,3-benzoselenadiazol-7-ylthiol (CLXXXV) 2,4,S-trichloroselenophenol (CLXXXVI) Z-naphthaleneselenol (CLXXXVII) l-(B-pentanamidophenyl)-tetrazol-5- ylselenol (CLXXXVIII) 1- 3-hexanamidophenyl) -tetrazol-5- ylselenol (C'L)Q(XIX) 1-(3-heptanamidophenyl)-tetrazol-5- ylselenol (CXC) l-(3-octanamidophenyl)-tetrazol-5-ylselenol (CXCI) l- 3-nonanamidophenyl) -tetrazol-5-ylselenol (CXCII) 1- S-decanamidophenyl -tetrazol-5-ylselenol (CXCIII) 1- 3-undecanamidophenyl) -tetrazol-5- ylselenol (CXCIV) l-(3-dodecanamidophenyl)-tetrazol-5- ylselenol (CXCIV) S-nitro-l,3-benzoselenazol-Z-ylselenol (CXCVI) 6-pentanamido-1,3-benzoselenazol-2- ylselenol (CXCVII) 6-octanamido-1,3-benzoselenazol-2- ylselenol (CXCVIII) 6-nonanarnido-1,3-benzoselenazol-2- ylselenol (CXCIV) 6-decanamido-l,3-benzoselenazol-Z-ylselenol (CC) 6-undecanamido-1,3-benzoselenazol-Z-ylselenol (CCI) 6-dodecanamido-l,3-benzoselenazol-2-ylselenol (CCII) S-pentanamido-1,3,4-selenadiazol-Z-ylselenol (CCIII) S-octanamido-1,3,4-selenadiazol-Z-ylselenol (CCIV) S-decanamido-l,3,4-selenadiazol-Z-ylselenol (CCV) S-octanamido-l,3,4-thiadiazol-2-ylselenol (CCVI) S-decanamido-l,3,4-thiadiazol-2-ylselenol (CCVII) 2-octylthio-1,3,4-thiadiazol-2-ylselenol (CCVIII) 2-pentylthio-1,3,4-thiadiazol-2-ylselenol (CCIX) 2-decylthi0-l,3,4-thiadiazol-2-ylselenol (CCX) 2-pentylthio-l,3,4-selenadiazol-Z-ylselenol (CCXI) 2-octylthio-1,3,4-selenadiazol-Z-ylselenol (CCXII) 2-decylthio-l,3,4-selenadiazol-Z-ylselenol (CCXIII) oXalic-bis-N- 3- 5 -mercaptotetrazo1- l-yl anilide] (CCXIV) suberic-bis-N- [3-(S-mercaptotetrazol-l-yl) anilide] (CCXV) terephthalic-bis-N-[3-(5-mercaptotetrazol- 1-yl)-anilide] CCXV I) disulfide,bis-l- 3-nonanamidophenyl tetrazol-l-yl (CCXVII) disulfide,bis-1-(3-hexanamidophenyl)- tetrazol-l-yl (CCVIII) disulfide,bis-6-octanamido-1,3-benzothiazol-Z-yl (CCXIX) disulfide,bis-6-pentanamido-1,3-benzothiazol-Z-yl (CCXX) disulfide,bis5-pentanamido-1,3,4-thiadiazol- (CCXXI) disulfide,bis-S-nonanamido-1,3,4-thiadiazol-Z-yl (CCXXII) disulfide,bis-Z-pentylthio-1,3,4-thiadiazol- (CCXXIII) disulfide,bis-2-octylthio-1,3,4-thiadiazol- (CCXXIV) 1- 3-octanamidophenyl) -5-mercaptotetrazole, sodium salt (CCXXV) l-(3-nonanamidopheny1)-5-mercaptotetrazole, potassium salt (CCXXVI) 2-octylthio-5-mercapto-1,3,4-thiadiazol,

ammonium salt (CCXXVII) Z-phenylthio-S-mercapto-1,3,4-thiadiazol In accordance with the invention, the bleach inhibitor is brought into contact with the silver sound image in a predominantly aqueous solution. The solution can be comprised of simply one or more bleach inhibitors present in the concentration range as described above. The solution, however, can contain other ingredients such as buffering agents to adjust the pH of the solution.

The pH of the solution can vary widely from mildly acidic of about pH 5 to strongly alkaline of about pH 12 or greater. Preferably, the pH of the solution is from about pH 6 to strongly alkaline and most preferably is from about pH 9 to pH 12.

The solution can also contain a water-soluble silver halide solvent or fixing agent such as potassium, sodium or ammonium sulfite, thiosulfate or thiocyanate or dithiooctanediol. The amount of fixing compound can range from as little as 0.05% W. or less of the solution to 30% w. or more of the solution. Preferably, the amount of fixing compound is from about 0.1% W. to about 2% W. of the solution. The presence of one or more of these fixing compounds in the solution is, however, not necessary.

The solution can contain a thickening agent to prevent the running of the solution into the picture area. Suitable thickening agents, for example, are a series of copolymers known as Gantrez available from GAP Corporation. Two examples are Gantrez ANl69 and Gantrez AN4651. Other suitable thickening agents are, for example, hydroxy ethyl cellulose and carboxy methyl cellulose. The quantity and type of thickening agent necessary to achieve the proper viscosity for the particular solution can be readily determined by those skilled in the art.

The bleach inhibitors used in the invention are known compounds and can be prepared by known methods. For example, the alkylamido substituted benzoxazoles, benZothiazoles and benzoselenazoles can be prepared by reacting the corresponding commercially available aminosubstituted compounds with an acid chloride. The 1-(3- al-kylamidophenyl)-5-mercaptotetrazoles are prepared by a similar method as shown in US. Pat. 3,376,310. Other bleach inhibitors can be prepared by methods available in well known organic chemistry reference works.

The selective treatment of only the sound track portion of the film can be accomplished by any convenient method. For example, the edge bearing the sound image can be passed through a bath containing the bleach inhibitor. A method particularly useful because many motion picture photofinishers have the necessary equipment is passing the sound area of the film under a roller (called a striping wheel) wet with a solution containing a bleach inhibitor.

The method of the invention is generally applicable to the production of sound track images in color films of any type in which dye images are formed or retained as a function of a developed latent silver halide image. Films of this type include those containing incorporated photographic couplers, a nondifiusible dye image being formed by reaction of a nonditfusible incorporated coupler with oxidized color developing agent resulting from development of the latent silved halide image. Also included are those not containing incorporated couplers, the latent silver halide image being developed with a coupler-developer composition and the nondiffusible dye image being formed from the reaction of the oxidized color developing agent and the coupler present in the coupler-developer composition. These films can be reversal print films or negative-positive print films.

The method of the invention is also applicable to the production of silver sound records in films in which the dye images are of a neutral density. Neutral density images can be formed from one or a mixture of couplers which react to form a neutral density dye or a combination of dyes which appear to be of neutral density. As with color image formation, subsequent to neutral density image formation, the silver of the picture record is removed by bleaching and fixing. The silver sound record can be retained in this type of film by the use of the bleach inhibitors to yield a neutral density film having a picture record comprised of a dye or a mixture of dyes and a sound record comprised of silver.

The method of our invention is useful to prevent the bleaching of silver sound records by both bleach compositions and bleach-fix compositions. Bleach compositions contain, for example, potassium dichromate or potassium ferricyanide as the oxidizing agent. Bleach-fix compositions are those which contain both an oxidizing agent such as an iron salt of EDTA and a fixing agent. In a bleach-fix composition the silver is oxidized to a silver salt which is then removed from the film all in a single solution. Bleaching compositions, however, only oxidize the silver to a silver salt. This silver salt and residual silver halide are subsequently removed by treatment with a separate fixing bath.

In general, bleaching compositions are more vigorous oxidizing compositions than bleach-fix compositions. For this reason it is preferred that the silver of the sound record be protected by a less hydrophilic bleach inhibitor during bleaching of the picture record silver with a bleach composition. Examples of such compounds are those which are substituted with a hydrophobic moiety such as a fatty chain. Compounds XXXVIII to XLVII, LIV to LXXXI CXCII to CXCIX and CCI to CCXVII are examples of typical fatty-substituted bleach inhibitors.

The terms picture record area and sound record area as used herein refer to areas of a motion picture film as these areas can be seen in a plane view. Along one or both edges of the film are sprocket perforations used to transport the film through motion picture printing and projecting apparatus. Occupying the major part of the area between the sprocket perforations or the performations and the opposite edge and are the individual frames containing the picture record. A narrow strip extending lengthwise along the film contains the sound record. These two areas are referred to as the picture record area and the sound record area, respectively.

The drawing depicts diagrammatically the processing of a typical negative-positive print element shown in crosssectional view to produce a color picture record having a silver sound record. With a reference to the embodiment in the drawing, support 22 has coated thereon gelatinosilver halide blue sensitive, yellow-forming layer 23, gelatino-silver halide red sensitive, cyan-forming layer 24 and gelatino-silver halide green sensitive, magentaforming layer 25. [For simplicity in illustrating the invention, conventional interlayers and overcoats have been omitted from the drawings. In stage 1, the element is exposed through the negative original depicted for simplification of the figure as a single layer 21 coated on transparent support 20. In practice, this original can be a multilayer element or a scene as viewed through a camera lens. Also, in practice, the picture record and the sound track record would generally be on separate originals and separate exposures made from each of these originals a short interval of time apart.

In carrying out a typical process of the invention as illustrated in the drawing, subsequent to exposure the latent image is developed in a color developer. The element then appears as in stage 2. Layers 23a, 24a and 25a in picture area 29 are comprised of silver and dye images. In picture area 28 these layers did not receive exposure and a latent image Was not formed. Area 28 of these layers is thus comprised of silver halide. Layers 24a and 25a in sound record area 26 are comprised of silver and dye according to exposure and are comprised of silver halide in sound record area 27 where no exposure occurred. Layer 23a did not receive sound exposure and is comprised of silver halide in both sound record areas. Subsequent to initial development and prior to bleaching, the element is contacted in sound record areas 26 and 27 with the bleach inhibitor. Stage 3 depicts the element subsequently to being contacted with bleach inhibitor. Picture record areas 28 and 29 not having been contacted with bleach inhibitor remain unchanged. The bleach inhibitor has diffused into layers 24b and 25b in sound record area 26 and has become absorbed to the silver present. Layer 23b remains unchanged. Stage 4 depicts the appearance of the element subsequent to bleaching and fixing or bleach-fixing. Layers 23c, 24c and 250 in picture area 28 are now clear, the residual silver halide having been removed. Picture area 29 in these layers is comprised of dye, the silver having been removed between stages 3 and 4. Sound record area 26 in layers 24c and 25c is comprised of silver and dye, the silver having been rendered unbleachable by the bleach inhibitor. Layer 230 in a sound record areas 26 and 27 and layers 24c and 250 in sound record area 27 are clear, the silver halide having been fixed out.

Certain of the bleach inhibitors used in the present process are useful for the preparation of silver sound tracks in the novel motion picture elements by the novel process disclosed and claimed in copending application of Bello and Holtz, entitled Film and Process Using Bleach Inhibitor for Producing Color Film With Silver Sound Record, Ser. No. 100,609, filed Dec. 22, 1970, now abandoned, and the continuation-in-part thereof filed concurrently herewith. The novel elements of this copending application are provided with an auxiliary layer coated outermost from the support and over the picture recording layers. This layer is of such photographic speed or spectral sensitivity or both that no image forms in the layer during picture image-forming 15 exposure of the underlying picture recording layers. Sound record exposure of the novel element is by the necessary Wavelengths of radiation and of suificient intensity to form a latent sound record image in at least the auxiliary layer. The so exposed element is then processed according to the disclosed novel process which comprises initial development of the latent image (either to a silver image in reversal print films or a silver and dye image in negative-positive print films), contacting the surface of entire film with a bleach inhibitor composition, reversal development if necessary, and bleach-fixing or bleaching and fixing. The processed element is comprised of a picture record comprised of dye and a sound record comprised of silver. The use of the novel element and process oifers the advantage that at no point in the processing of the element must the sound track or picture record areas of the element be given individual treatment. This is possible because of the auxiliary layer of the element. In the picture record area of the element, the auxiliary layer is not exposed. During initial development the silver halide in this area of this layer does not develop to metallic silver. However, in the sound track area a latent image is formed and is developed to metallic silver. When the element is contacted with bleach inhibitor composition the bleach inhibitor diffuses into and through the auxiliary layer in those areas where metallic silver was developed (the sound track area) much faster than in those areas where only silver halide is present (the picture area). As a result of this diiferential rate of diffusion of bleach inhibitor through the silver and silver halide of the auxiliary layer, only the silver of the sound track area is contacted with bleach inhibitor and is protected from the bleaching action of the bleach or bleach-fix solutions. Because the bleach inhibitor diffuses more slowly through silver halide, the picture record silver in the underlying layers is not contacted with bleach inhibitor and remains bleachable. It is, therefore, subsequently bleached and fixed out.

Certain of the bleach inhibitors used in the present process can be substituted onto photographic color couplers in the coupling position through the thiol or selenol group. These couplers can then be incorporated into an auxiliary silver halide layer similar to that described immediately above coated on a novel photographic element which is exposed to a picture and sound record and chromogenically developed. The oxidized color developer resulting from development of the latent sound record in the auxiliary layer reacts with the incorporated bleach inhibitor substituted coupler to couple ofi a moiety which forms a bleach inhibitor. This image-wise released bleach inhibitor contacts the developed silver of the sound record in at least the auxiliary layer and renders it unbleachable. The auxiliary layer in the picture area is not exposed. Consequently, no development takes place in this area of the auxiliary layer and bleach inhibitor is not released. Therefore, all silver formed in the picture area remains bleachable. The processed element is comprised of a picture record comprised of dye and a sound record comprised of silver. The novel photographic element containing these incorporated bleach inhibitor-substituted couplers and the process for producing a motion picture film having a silver sound record from this element are disclosed and claimed in copending application Holtz, entitled Film Containing Bleach Inhibitor Releasing Compounds and Process for Preparing Auxiliary Silver Image or Silver Sound Record Therewith, Ser. No. 100,610, filed Dec. 22, 1970, now abandoned, and the continuationin-part thereof filed concurrently herewith.

Certain of the bleach inhibitors used in the present process can be incorporated into an auxiliary silver halide layer similar to that described above coated on a novel photographic element. The bleach inhibitors are incorporated as the free bleach inhibitor rather than substituted on a coupler as described above. The exposed element is chromogenically developed. The bleach inhibitor present in the auxiliary layer becomes adsorbed to the 16 silver developed up in the sound record area. The picture area of the auxiliary layer not having been exposed contains only residual silver halide. Thus, only the silver of the sound record in the auxiliary layer is protected from bleaching. The processed element is comprised of a picture record comprised of dye and a sound record comprised of silver. The novel photographic element containing these incorporated bleach inhibitors and the process for producing a color film having an integral silver sound record from this element are disclosed and claimed in copending application Lestina, Kent, Holtz, entitled Film Containing Bleach Inhibitor and Process Therefor for Producing Color Film With Silver Sound Record," Ser. No. 100,613, filed Dec. 22, 1970, and the continuation-in-part thereof filed concurrently herewith.

The following examples are included for a further understanding of the invention.

EXAMPLE 1 Silver metal particles of about 0.12 micron are prepared by contacting a silver nitrate solution with a reducing agent comprised of sodium citrate and ferrous sulfate. These particles are dispersed at a concentration of 3 10- molar in 0.05% w. aqueous gelatin. Bleach inhibitor baths are prepared by dissolving the bleach inhibitor in water at about 10- to 10- molar, adjusting the pH as indicated and diluting to a bleach inhibitor concentration of 10' mole One volume of the reduced silver-gelatin dispersion is mixed with one volume of bleach inhibitor bath. To this mixture is added one volume of Bleach-Fix Bath I, described above. Bleach-fixing occurs when the mixture changes from dark brown to colorless, which. takes four minutes when no bleach inhibitor is present. The compounds listed in Table I inhibit bleach-fixing for a minimum of fifteen minutues (i.e., 11 minutes longer than the control) at the pH indicated.

TABLE I Bleach inhibitor: pH Z-mercaptolauric acid 10.1 Z-mercaptoacetanilide 10.1 2,4,5-trichlorothiophenol 1 1.2 Z-quinolinylthiol 4.6, 7.3, 10.0 2-naphthalenethio1 6.5 and basic 1-phenyl-5-selenotetrazole 6.0 1-phenyl-5-mercaptotetrazole 2,7 and 10 1-(3 heptafluorobutanarnidophenyl)- 5-mercaptotetrazole 9.8 1-{3-[(2,4-di-tert-amylphenoxy) acetamido1-phenyl} 5 mercaptotetrazole 6.5, 11.3 1-(4-methoxybenzoyl) 5 mercaptotetrazole 8.85 1- [4-(piperidinylsulfony1) phenyl1-5- mercaptotetrazole 9.7 1-(4-fluorophenyl)-5 mercaptotetrazole 9.75 1-(3-trifluoromethylphenyl) 5 mercaptotetrazole 10:5 1-(l-naphthyl)-5-mercaptotetrazole 9.7 1-(2-naphthyl)-5-mercaptotetrazole 9.7 1-(4-cyanophenyl)-5 mercaptotetrazole 10.3 1-hexyl-S-mercaptotetrazole 9.9 '3-mercapto-4-phenyl 5 n undecyl- 1,2,4-triazole 9.95 3 (5-mercapto-1,2,4-triazol-3 ylthio) propanoic acid 3.61, 9.97 Z-mercaptobenzothiazole 10.6, 6.5 6-ethoxy-2-mercaptobenzothiazole 10.1 5-chloro-2-mercaptobenzothiazole 10.1 2-benzoxazolethiol 10.7 2-nonanamido-5-mercapto-1,3,4 thiadiazole 6.5 2-nonanamido-6-mercaptopurine 11.4

The above results demonstrate that a variety of com pounds are excellent bleach inhibitors. These compounds, when applied to the silver sound record of a developed photographic gelatino silver halide layered element containing a silver picture record and a silver sound track record, satisfactorily inhibit the bleaching of the sound track silver during bleaching of the picture record silver under the conditions described above.

EXAMPLE 2 Silver metal particles of about 0.12 micron are prepared by contacting a silver nitrate solution with a reducing agent comprised of sodium citrate and ferrous sulfate. These particles are dispersed at a concentration of 6X10- molar in 0.05% w. aqueous gelatin. Bleach inhibitor baths are prepared by dissolving the bleach inhibitor in water, adjusting the pH to 7, diluting to a concentration of 10- molar and combining this solution with an equal volume of 10- molar aqueous potassium iodide solution. To one volume of silver dispersion is added two volumes of bleach inhibitor followed by the addition of one volume of Bleach-Fix Bath I, described above. The bleaching and fixing of the metallic silver is followed spectrophotometrically at 425 nm. Bleach-fix time is the time in minutes required for. the density of the dispersion to decrease to 0.05 density units above background density of the bleach-fix solution. The compounds listed in Table 11 result in bleachfixing times as indicated.

TABLE II Bleach-fix Bleach inhibitor: time (min.) Control (no bleach inhibitor) 1.5

The above results demonstrate that a variety of compounds are efiective as silver bleach inhibitors and are capable of preventing bleaching for up to days. These compounds, when applied to the silver sound record of a developed photographic gelatino silver halide layered element containing a silver picture record and a silver sound track record, satisfactorily inhibit the bleaching of the sound track silver during bleaching of the picture record silver under the conditions described above.

EXAMPLE 3 A film bearing a fine-grain gelatino silver halide emulsion is sensitometrically exposed, developed, treated with a stop bath, fixed, hardened and washed in the conventional manner. A portion (A) of the film is dried. A second portion (B) is treated for 1 minute at 20 C. with a solution containing 40 g./l. of potassium octyl xanthate. A third portion (C) is treated for 1 minute at 20 C. with a solution containing 40 g./l. of potassium octyl xanthate and 300 g./l. of sodium thiosulfate crystals. A fourth 18 portion (D) is left untreated. Portions B, C and D are washed, bleached with a ferricyanide bleach similar to that of Example 9, step 14, fixed, washed and dried. The maximum (D and minimum (D silver densities for each portion of the film is shown in Table HI below.

TABLE III Dmin. Dmnx.

Film portion:

The above data demonstrate the effectiveness of potassium octyl xanthate in preventing the bleaching of a developed silver record. It also demonstrates increased effectiveness of certain bleach inhibitors is obtained when the bleach inhibitor solution contains a silver halide solvent or fixing agent. Treatments (B) and (C) are thus useful for preventing the bleaching of silver when applied to the silver sound record of a developed photographic gelatino silver halide layered element containing a silver picture record and a silver sound track record under the described conditions.

EXAMPLE 4 Strips of a multilayer color photographic motion picture negative-positive print film (Eastman Color Print Film, Type 5385, 35 mm.) with a picture record area and a sound track record area and bearing three gelatino silver halide color forming units sensitive to the blue, green and red regions of the visible spectrum and having nondiffusible photographic couplers capable of forming nondiifusible yellow, magenta and cyan dye images, respectively, are sensitometrically exposed in both picture and sound areas and processed as follows: 1) Prebath 15 sec. (2) Wash 15 sec. (3) Color develop 9 min. (4) Stop bath 2 min. (5) Wash 1 min. (6) Remove surface water Air blast. (7) Bleach inhibitor application 40 sec. (8) Bleach-fix 2 min. (9) Wash 6 min. (10) Stabilize 10 sec. (11) Dry Process temperature 24 C. The chemical composition of the above baths is as follows:

(1) PREBATH Borax (Na B O -10H O) ..g 20 Sodium sulfate, desiccated g Sodium hydroxide, 10% solution ml 10 Water to make 1 liter.

(3) COLOR DEVELOPING COMPOSITION G. Sodium hexamethaphosphate 2 Sodium sulfite, desiccated 4 Z-amino-S-diethylaminotoluene, monohydrochloride 3 Sodium carbonate, monohydrated 20 Potassium bromide 2 Water to make 1 liter.

(4) STOP BATH Acetic acid, glacial ml- 24.5 Sodium bisulfite g 6.4 Water to make 1 liter (pH 3.7 6).

19 7 BLEACH INHIBITOR BATH Gantrez AN 169 (A copolymer of maleic anhydride and methyl vinyl Water to make 1 liter.

The bleach inhibitor bath is applied to the sound track area of the film only. A control strip is prepared by processing according to steps 1 to 3 above followed by fixing according to step 4 of Example 5 and drying. The silver density of the strips is measured on a densitometer at 900 nm. The results are set forth in Table IV below.

TABLE IV Silver density in sound track area Concen- Percent tration, Bleach silver grams] inhibitor density Bleach inhibitor liter treated Control retained Z-merceptobenzothiazoL. 15 1. 58 2.10 76 1-phenyl-5-mercaptotetrazole 2 1. 50 2. 71 Do 20 1. 52 2. 10 72 1-(3-acetemidophenyl)-5- mercaptotetrazole 1. 61 2. 10 72 D0 1 2.14 2.10 100 The above results show that the bleach inhibitors effectively inhibit bleaching of the silver sound record when applied over a wide range of concentrations. The silver densities retained in the bleach inhibitor treated sound track areas represent more than sufiicient silver density for an excellent sound track. A sound track should have an infrared density at 800 mm. of about 1.2 to 1.4 to give satisfactory results for the life of the film. The silver is substantially completely removed in the picture record area. When the same film is exposed to a picture and sound record and processed as above using the above bleach inhibitors, dye picture records substantially completely free of silver and excellent silver sound records are obtained.

EXAMPLE 5 When the procedure of Example 4 is repeated except that a fixing bath of the composition set forth below is substitued for the step 4 stop bath and a 1 /2 minute bleach-fix bath of the following composition is substituted for the step 8 bleach-fix bath the results set forth in Table V are obtained. The control sample is prepared by omitting steps 6 through 9 of the process.

20 (4) FIX BATH Sodium thiosulfate g 240 Sodium sulfite, desiccated g 15 Acetic acid, 28% ml 48 Boric acid, crystals 7 5 Q Potassium alum g 15.0 Water to make 1 liter.

(8) BLEACH-FIX BATH Sodium Iron Salt of ethylenediaminetetraacetic acid g 60 Sodium sulfite g 12 Ammonium thiosulfate (60% solution) ml 200 Tetrasodium salt of ethylenediaminetetraacetic acid g 6.7 Ammonium thiocyanate g.. 12

Water to make 1 litre.

The bleach inhibitor used for this run is Z-mercaptobenzothiazole. The results shown in Table V demonstrate the effects of varying the bleach inhibitor contact time and concentration widely. The results set forth in Table V are silver densities at 900 nm. The control sample silver density is 2.38.

TABLE V Concentration, grams/liter Bleach inhibitor contact time 1 2 5 10 seconds 1. 71 1. 62 1. 20 seconds 1. 75 1. 70 1. 66 40 seconds 1. 71 1. 65 1. 79

The above two examples demonstrate that sufiicient silver density is retained in the sound record during the bleachfixing of a developed photographic silver halide element to remove silver from the picture record area when the sound record silver is protected by the bleach inhibitors. In the above examples, the silver density of those areas of the film not contacted with bleach inhibitor is less than 0.1. These results also demonstrate that bleach inhibitor contact time can vary widely and not substantially effect the results obtained.

EXAMPLE 6 Strips of the same multilayer color negative-positive print film used in Examples 4 and 5 are sensitometrically exposed and processed as follows:

Process baths 1, 3, 7 and 12 are the same as process baths 1, 3, 7 and 10, respectively of Example 4. Fix baths 4 and '10 are the same as fix bath 4 of Example 5. Bleach bath 8 has the following composition:

G. Potassium bromide 20 Potassium dichromate 5 Potassium alum 40 Water to make 1 liter.

The results shown in Table VI demonstrate the bleach inhibitors etfectively prevent the bleaching of a silver sound record while the picture record silver, which is not contacted with bleach inhibitor, is bleached. The silver density of those areas of the film not contacted with bleach inhibitor are less than 0.1.

TABLE VI Silver density Concen- Percent tration, Bleach silver grams] inhibitor density Bleach inhibitor liter treated Control retained fi-nonanamidomercapto benzothiazole 5 2. ll 2. 10 100 1-(3-decanamldophenyD- B-mercaptotetrazole 6 2. l 2. 10 100 EXAMPLE 7 A multilayer color film with a picture record area and a sound track record area and bearing three color image color-forming units similar to the films of Examples 4 to 6 but containing in addition an overcoat layer comprising a gelatino silver chlorobromide (80 mole percent chloride and 20 mole percent bromide) emulsion having an average grain size of about 0.1 micron coated at 25 mgJft. silver and 113 mg./ft. gelatin, and containing 45 mgJft. magenta coupler 1-(6-chloro-2,4-dimethylphenyl)-3-[u- (m-pentadecylphenoxy)-butyramido]--pyrazoloue (US. Pat. 3,062,653 at lines to 20, column 4) is exposed for ,5 second through a Wratten 18-A filter (transmit radiation of 300 to 400 nm.) to a step tablet in the sound track area, and for V 0 second through a filter pack which results in a nearly neutral density exposure to a 21 step 0.15 log E increment step tablet in the picture area and processed in the following baths:

Baths 1, 3, 5, 9 and 11 above have the same composition as baths 1, 3, 4, 8 and 10, respectively, of Example 4. Bleach inhibitor bath 7 has one of the following four compositions. The pH of the baths is adjusted with sodium hydroxide or sulfuric acid to the indicated value.

BATH 7A Bleach inhibitor moles 1.55 x10- Sodium carbonate, monohydrate g 6.2 Water to make 1 liter. pH adjusted to 10.0.

7 BATH 713 Bleach inhibitor moles 1.55 X 10" Sodium carbonate, monohydrate g 6.2 Sodium sulfite g 6.3 Water to make 1 liter. pH adjusted to 10.0.

BATH 7C Identical to Bath 7A except pH adjust to 12.1.

BATH 7D Identical to Bath 7B except pH adjusted to 12.1.

Only the sound record silver is contacted with bleach inhibitor during step 7. Those areas of the film not contacted with the bleach inhibitor are substantially free of silver. The results set forth in Table VII demonstrate several diflerent bleach inhibitors efifectively inhibit the bleach-fixing of the silver sound record. The silver densities are measured in the same manner as in Example 4.

TABLE VII Sound record Bleach silver inhibitor Bleach inhibitor density bath 1-(3-nonanamidophenyl)-5-mercaptotetrazole 2.92 7A -(3-deeanamidophenyl)-5-mercaptotetrazole 231 7A l-(3-undecanamidophenyl)-5-mercaptotetrazol 2. 04 7A 2-nonanamido-B-mercaptothiadiazole, 2.00 7!. 2-nonanamido-5-mercapto-1,3,4-triazole 2.28 7A 6-nonauamido-2-mercaptobenzothiazole 2.37 7A Z-mercaptolaurie acid 1.90 7A fi-nonanamido-l 3-benzimidazol-2-ylthiol 2. 26 7C 1-(3-heptanamido henyl)-5-rnereaptotetrazole. 2.78 7B 1-(3-octanamidop enyl)-5-mereaptotetrazole 2.78 7B l-(3-nonanamidophenyl)-5-mercaptotetrazole 2. 62 7B 6-heptanamido-Z-mercaptobenzothiazole 2.72 7B 1-(3-suberamldophenyl)-6-mereaptotetrazole 2. 88 7B 2-quinoliny1thiol 1.68 7B Naphthalenethiol. 1.45 7D The above results demonstrate these various compounds are excellent bleach inhibitors. When the same film is exposed to a picture and sound record and processed as above using the above compounds as bleach inhibitors, films are obtained having picture records substantially free of silver and excellent silver sound records.

EXAMPLE 8 A multilayer motion picture color print film similar to that of Example 4 is exposed to picture and sound negatives and processed according to the procedure of Example 4. Bleach inhibitor bath 7 contains 0.4 g./liter l-(3-nonanamidophenyl)-5-mercaptotetrazole as bleach inhibitor. In step 7 bleach inhibitor bath is applied to only the sound record silver. The sound record silver remains substantially unaffected by the bleach-fixing bath. The processed film when projected by a sound projector gives an excellent picture record and sound record.

EXAMPLE 9 Ektachrome reversal print film, Type 7388, sold by Eastman Kodak Company, having three color-forming gelatino silver halide units sensitive to the blue, green and red regions of the visible spectrum and having photographic couplers capable of forming yellow, magenta and cyan dye images, respectively, is exposed to a picture rec- 23 ord positive and a sound record negative and processed according to the following procedure:

Tempera- Bath Time ture, C.

1. Prehardener 2 minutes, 30 seconds- 35 2. Neutralizer- 30 seconds 35 3. First developer 2 minutes, 15 seeonds 3B 4. First stop 30 seconds 35 6. Wash 30 seconds 38 6. Fix sound track 2 minutes- 38 7. Hypo eliminator- 20seconds 38 8. Wash 30 seconds 38 9. Color developer-. minutes- 38 10. Second stop 30 seconds 35 11. Was 30= 38 Remove surface water-air blast 12. Bleach inhibitor application.... 1 minute 38 13. Wash 30 seconds 38 14. Bleac 1 minute, 30 seconds.-. 35

15. Fix.... 1 minute, 30 seconds 35 16. Wash 1 Ininu 38 17. Stabilizer 30 seconds 35 The chemical composition of the above baths is as follows:

( 1 PREHARDENER Water ml 800.0 p-Toluenesulfinic acid (sodium salt) g.. 1.0 Succinaldehyde, bis, bisulfite g-. 8.5 Magnesium sulfate, heptahydrate g 257.0 Sodium sulfate g.. 75.0 Sodium bromide g- 2.0 Sodium acetate g 15.0

Formalin (37% by volume aqueous formaldehyde solution) ml 27.0 Glacial acetic acid ml 2.4 N-Methyl benzothiazolium-p-toluene sulfonate .03 Water to 1.0 liter. g

(2) NEUTRALIZ'ER Water ml 800.0 Hydroxylamine sulfate g 18.0 Sodium bromide g.. 17.0 Glacial acetic acid ml 10.0 Sodium hydroxide g 6.8 Sodium sulfate g 50.0 Water to 1.0 liter.

(3) FIRST DEVELOPER Water ml 800.0 Sodium tetraphosphate g 2.0 Sodium bisulfite g 8.0 1-phenyl-3-py1'azolidone g .35 Sodium sulfite g 37.0 Hydroquinone g 5.5 Sodium carbonate (anhydrous) g 28.2 Sodium thiocyanate g 1.38 Potassium iodide (0.1% by weight aqueous solution) ml 13.0 Sodium bromide g 1.30 Water to 1.0 liter.

(4) AND (10) FIRST AND SECOND STOP BATH Water ml 800.0 Glacial acetic acid "ml-.. 30.0 Sodium hydroxide g 1.65 Water to 1.0 liter.

(6) SOUND TRACK FIX Kelgin MV (a Kelgin derivative thickener sold by Kelco Company) g 3.0 Ammonium thiosulfate (60% sol.) ml 400.0 Sodium sulfite g 20.0 Hexylene glycol ml 3.0 Water to make 1 liter.

Adjust to pH 4.5.

24 (7) HYPO ELIMINATOR Sodium hypochlorite (5%% solution) ml 15 Sodium tetraborate g 14.5 Water to make 1 liter.

(9) COLOR DEVELOPER Water ml 800.0 Nitrilo (trimethylene phosphonic acid) sodium salt ml 3.0 Benzyl alcohol g 4.5 Sodium sulfite g 7.5 Trisodium phosphate-EH 0 g 36.0 Sodium bromide g 0.9 Potassium iodide (0.1% w. sol.) ml Sodium hydroxide g 3.25 Citrazinic acid g.. 1.5 4-amino-3-methyl-N-ethyl N- (beta methanesulfonamidoethyD-aniline sesquisulfate monohydrate g 11.0 Tertiarybutylamine borane 0.07 Ethylenediamine g 3.0 Water to make 1.0 liter.

(12) BLEACH INHIBITOR BATH G. S-mercapto-Z-n-octylthio-1,3,4-thiadiazole 15.0 Gantrez AN 4651 6.25 Sodium hydroxide 40.0

Water to make 1.0 liter.

Gantrez AN 4651 is a copolymer of methyl vinyl ether and maleic anhydride added as a thickening agent available from GAF Corporation.

(14) FERRICYANIDE BLEACH Water ml 800.0 Sodium bromide g 43.0 Sodium ferrocyanide (decahydrate) g 245.0 Potassium persulfate g.. 67.0 Borax (Na B O -5H O) g 1.0

Carbowax 1540 (a polyethylene glycol sold by Water to 1.0 liter.

Step 6 sound track fix and step 12 bleach inhibitor application are to the sound record only. The sound record silver remains substantially unalfected by the bleach and second fix baths. The processed film when projected by a sound projector gives an excellent color picture record and a silver sound record superior to that obtained from the same film by sulfiding the sound record by conventional means.

The invention has been described in detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

We claim as our invention:

1. In the process of producing a picture record and an auxiliary silver image record in an exposed photographic element having at least one silver halide emulsiOn layer'which comprises developing said exposed element to form a picture record comprising silver and dye and an auxiliary image record comprising silver and bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the auxiliary image but not the silver of the picture record prior to bleaching with a silver bleach inhibitor which retains at least a portion of the silver of the auxiliary image record during said bleaching.

2. The improvement of claim 1 wherein said bleach inhibitor has an acidic thiol or selenol group.

3. The improvement of claim 1 wherein said bleach inhibitor has a formula selected from the group consisting of:

a represents 0, 1, 2, 3, 4, or 6;

X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represents a member selected from the group consisting of nitro, halo, an alkyl group, an aryl group, a thio group containing from 3 to 22 carbon atoms, an amido group containing from 4 to 22 carbon atoms, a carbonyl group, a carbamoyl group, an alkoxy group and an aryloxy group;

R represents a member selected from the group consisting of hydrogen and an acyl group;

Y represents a basic cation;

A A A and A each represents a member selected from the group consisting of a carbonyl group, a thiocarbonyl group, a carboxymethylene group, a 3 to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ring containing at least one carbon atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and selenium such that R R R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent a carbonyl group or a thiocarbonyl group and such that the grouping N t-A the grouping R tA -l, the grouping N t-A and the grouping R ,,{-A each represents a moiety having a molecular weight of from 100 to 1,000.

4. The improvement of claim 3 wherein R A l, R tA -l, R d-A and R .,,{-A represent a member se lected from the group consisting of a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus, a thiadiazole nucleus, a triazole nucleus and a l-phenyltetrazole nucleus.

5. The improvement of claim 1 wherein said bleach inhibitor is selected from the group consisting of a mercaptoalkanoic acid, a xanthate, a thioaryl and a mercaptosubstituted heterocyclic compound containing 5 to 6 atoms in the ring, said ring containing at least one nitrogen atom.

6. The improvement of claim 5 wherein said bleach inhibitor is selected from the group consisting of a mercaptobenzoxazole, a mercaptobenzothiazole, a mercaptobenzimidazole, a mercaptothiadiazole, a mercaptotriazole and a 1-phenyl-5-mercaptotetrazole.

7. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having at least one silver halide emulsion which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, and bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching With a silver bleach inhibitor which retains at least a portion of the silver of the sound track during said bleaching.

8. The improvement of claim 7 wherein said photographic silver halide element contains at least one nondift'using photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondiffusing dye.

9. The improvement of claim 8 wherein said bleach inhibitor has an acidic thiol or selenol group.

10. The improvement of claim 8 wherein said bleach inhibitor is selected from the group consisting of a mercaptoalkanoic acid, a xanthate, a thioaryl and a mercaptosubstituted heterocyclic compound containing 5 to 6 atoms in the ring, said ring containing at least one nitrogen atom.

11. The improvement of claim 10 wherein said bleach inhibitor is selected from the group consisting of a mercaptobenzoxazole, a mercaptobenzothiazole, a mercaptobenzimidazole, a mercaptothiadiazole, a mercaptotriazole and a 1-phenyl-5-mercaptotetrazole.

12. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor which retains at least a portion of the silver of the sound record during said bleachmg.

13. The improvement of claim 12 wherein said sensitive photographic silver halide element contains in each of said superposed ditferently sensitized layers at least one nondifiusing photographic color coupler which reacts with oxidized aromatic primary amine color developing agent to form a nondilfusing dye.

14. The improvement of claim 13 wherein said dye formed during said development is a subtractive dye essentially complementary in color to the sensitivity of the emulsion in which it is incorporated.

15. The improvement of claim 14 wherein said bleach inhibitor has an acidic thiol or selenol group.

16. In the process of producing a color picture record and a silver sound track record in an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record prior to bleaching with a silver bleach inhibitor having a formula selected from the group consisting of:

a represents 0, 1, 2, 3, 4, 5 or 6;

X represents a member selected from the group consisting of sulfur and selenium;

R R R and R each represents a member selected from the group consisting of nitro, halo, an alkyl group, an aryl group, a thio group containing from 3 to 22 carbon atoms, an amido group containing from 4 to 22 carbon atoms, a carbonyl group, a carbamoyl group, an alkoxy' group and an aryloxy group;

R represents a member selected from the group consisting of hydrogen and an acyl group;

Y represents a basic cation;

27 A A A and A each represents a member selected from the group consisting of a carbonyl group, a thiocarbonyl group, a carboxymethylene group, a 3 to 6 membered carbocyclic ring and a 3 to 6 membered heterocyclic ring containing at least one carbon atom and at least one heteroatom selected from the group consisting of nitrogen, oxygen, sulfur and selenium such that R R R and R do not represent a carbonyl group, a carbamoyl group or an amido group when A A A and A represent a carbonyl group or a thiocarbonyl group and such that the grouping and the grouping Rflfl-A each represents a moiety having a molecular weight of from 100 to 1,000.

17. The improvement of claim 16 wherein R A R -A R tA -t and Rfl-AQ represent a member selected from the group consisting of a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus, a thiadiazole nucleus, a triazole nucleus and a 1-phenyltetrazole nucleus.

18. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor selected from the group consisting of a mercaptobenzoxazole, a mercaptobenzothiazole, a mercaptobenzimidazole, a mercaptothiadiazole, a mercaptotriazole and a 1-phenyl-5-mercaptotetrazole, which retains at least a portion of the silver of the sound record during said bleaching.

19. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor having the following forwherein n represents a positive integer of from to and R represents an alkyl group having from 1 to 17 carbon atoms, which retains at least a portion of the silver of the sound record during said bleaching.

20. The improvement of claim 19 wherein n represents 1 and R represents an alkyl group having from 5 to 10 carbon atoms.

21. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor having the following formula:

o R ii-N SH 1 8 wherein n represents a positive integer of from 0 to 5 and R represents an alkyl group having fom 1 to 17 carbon atoms, which retains at least a portion of the silver of the sound record during said bleaching.

22. The improvement of claim 21 wherein n represents 1 and R represents an alkyl group having from 5 to 10 carbon atoms.

23. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor having the following formula:

O (R"( l-N it wherein n represents a positive integer of from 0 to 5 and R represents an alkyl group having from 1 to 17 carbon atoms, which retains at least a portion of the silver of the sound record during said bleaching.

24. The improvement of claim 23 wherein n represents 1 and R represents an alkyl group having from 5 to 10 carbon atoms.

25. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor having the following formula:

N-N Hall 3.2-1.

wherein Z represents a member selected from the group consisting of sulfur and the group -NHCO- and R represents an alkyl group havingfrom 5 to 17 carbon atoms, which retains at least a portion of the silver of the sound record during said bleaching.

26. The improvement of claim 24 wherein R represents an alkyl group having from 8 to 12 carbon atoms.

27. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, difierently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching 29 with a silver bleach inhibitor having the following formula:

wherein R represents an alkyl group having from to 17 carbon atoms, which retains at least a portion of the silver of the sound record during said bleaching.

28. The improvement of claim 27 wherein R represents an alkyl group having from 8 to 12 carbon atoms.

29. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, differently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, bleaching and fixing the element to remove the silver of the picture record; the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with a silver bleach inhibitor having the following formula:

30 wherein n represents a positive integer of from 0 to 5 and R represents an alkyl group having from 1 to 17 carbon atoms which retains at least a portion of the silver of the sound record during said bleaching.

30. The improvement of claim 29 wherein n represents 1 and R represents an alkyl group having from 5 to 10 carbon atoms.

31. In the process of producing a color picture record and a silver sound track record on an exposed photographic element having a plurality of superposed, dififerently sensitized silver halide layers which comprises developing said exposed element to form a picture record comprising silver and dye and a sound track record comprising silver, the improvement which comprises contacting the silver of the sound track record but not the silver of the picture record prior to bleaching with an aqueous bleach inhibitor bath comprised of 0.4 g./liter 1-(3-nonanamidophenyl)5-mercaptotetrazole having pH 12.1.

References Cited UNITED STATES PATENTS 3,083,097 3/1963 Lassig et a1. 9629 L 3,210,189 10/1965 Von Watburg 9659 DAVID KLEIN, Primary Examiner A. T. SUROPICO, Assistant Examiner US. Cl. X.R. 9660 R (5/69) uivmmu 0111 111132) lifiilfilwji Urrmlm,

CERTEFEQATZE W5 @WRREQTEQN Patent No. 3 9 705 2 8 03 Dated December 12 1 972 Michael J. Bevis, Hobson J. Bello, and Carl F. Holtz Inventor(s) I It; is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 26, lines 50-51 (Claim 16), delete after silver" "and dye and a sound track record comprising silver" Column 26, line 54' (Claim 16) after "0rd" insert -but not the silver of the picture record-'-.

Signed and sealed this 10th day of July 1973.

(SEAL) Attest;

EDWARD M.PLETCHER,-J R. Rene Tegtme-yer v Attesting Officer Acting Commissioner of Patents 

